IPCS INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY
Health and Safety Guide No. 28
PHOSPHINE
AND SELECTED METAL PHOSPHIDES
HEALTH AND SAFETY GUIDE
UNITED NATIONS ENVIRONMENT PROGRAMME
INTERNATIONAL LABOUR ORGANISATION
WORLD HEALTH ORGANIZATION
WORLD HEALTH ORGANIZATION, GENEVA 1989
This is a companion volume to Environmental Health Criteria 73:
Phosphine and selected metal phosphides
Published by the World Health Organization for the International
Programme on Chemical Safety (a collaborative programme of the United
Nations Environment Programme, the International Labour Organisation,
and the World Health Organization)
This report contains the collective views of an international group of
experts and does not necessarily represent the decisions or the stated
policy of the United Nations Environment Programme, the International
Labour Organisation, or the World Health Organization
ISBN 92 4 154349 3
ISSN 0259-7268
The World Health Organization welcomes requests for permission to
reproduce or translate its publications, in part or in full.
Applications and enquiries should be addressed to the Office of
Publications, World Health Organization, Geneva, Switzerland, which
will be glad to provide the latest information on any changes made to
the text, plans for new editions, and reprints and translations
already available.
(c) World Health Organization 1989
Publications of the World Health Organization enjoy copyright
protection in accordance with the provisions of Protocol 2 of the
Universal Copyright Convention. All rights reserved.
The designations employed and the presentation of the material in this
publication do not imply the expression of any opinion whatsoever on
the part of the Secretariat of the World Health Organization
concerning the legal status of any country, territory, city or area or
of its authorities, or concerning the delimitation of its frontiers or
boundaries.
The mention of specific companies or of certain manufacturers'
products does not imply that they are endorsed or recommended by the
World Health Organization in preference to others of a similar nature
that are not mentioned. Errors and omissions excepted, the names of
proprietary products are distinguished by initial capital letters.
CONTENTS
INTRODUCTION
1. PRODUCT IDENTITY AND USES
1.1. Identity
1.2. Physical and chemical properties
1.3. Analytical methods
1.4. Production and uses
2. SUMMARY AND EVALUATION
2.1. Human exposure to phosphine and metal phosphides
2.2. Fate in the environment
2.3. Uptake, metabolism, and excretion
2.4. Effects on organisms in the environment
2.5. Effects on animals and human beings
3. CONCLUSIONS AND RECOMMENDATIONS
4. HUMAN HEALTH HAZARDS, PREVENTION AND PROTECTION, EMERGENCY
ACTION
4.1. Main human health hazards, prevention and protection,
first aid
4.1.1. Advice to physicians
4.1.2. Health surveillance advice
4.2. Explosion and fire hazards
4.3. Storage
4.4. Transport
4.5. Spillage and disposal
5. HAZARDS FOR THE ENVIRONMENT AND THEIR PREVENTION
6. INTERNATIONAL CHEMICAL SAFETY CARD
7. CURRENT REGULATIONS, GUIDELINES, AND STANDARDS
7.1. Exposure limit values
7.2. Specific restrictions
7.3. Labelling, packaging, and transport
BIBLIOGRAPHY
INTRODUCTION
The Environmental Health Criteria (EHC) documents produced by the
International Programme on Chemical Safety include an assessment of
the effects on the environment and on human health of exposure to a
chemical or combination of chemicals, or physical or biological
agents. They also provide guidelines for setting exposure limits.
The purpose of a Health and Safety Guide is to facilitate the
application of these guidelines in national chemical safety
programmes. The first three sections of a Health and Safety Guide
highlight the relevant technical information in the corresponding EHC.
Section 4 includes advice on preventive and protective measures and
emergency action; health workers should be thoroughly familiar with
the medical information to ensure that they can act efficiently in an
emergency. Within the Guide is an International Chemical Safety Card
which should be readily available, and should be clearly explained, to
all who could come into contact with the chemical. The section on
regulatory information has been extracted from the legal file of the
International Register of Potentially Toxic Chemicals (IRPTC) and from
other United Nations sources.
The target readership includes occupational health services, those in
ministries, governmental agencies, industry, and trade unions who are
involved in the safe use of chemicals and the avoidance of
environmental health hazards, and those wanting more information on
this topic. An attempt has been made to use only terms that will be
familiar to the intended user. However, sections 1 and 2 inevitably
contain some technical terms. A bibliography has been included for
readers who require further background information.
Revision of the information in this Guide will take place in due
course, and the eventual aim is to use standardized terminology.
Comments on any difficulties encountered in using the Guide would be
very helpful and should be addressed to:
The Manager
International Programme on Chemical Safety
Division of Environmental Health
World Health Organization
1211 Geneva 27
Switzerland
THE INFORMATION IN THIS GUIDE SHOULD BE CONSIDERED AS A STARTING POINT
TO A COMPREHENSIVE HEALTH AND SAFETY PROGRAMME
1. PRODUCT IDENTITY AND USES
1.1 Identity
Phosphine
Chemical formula: PH3
Structural formula: H
'
P - H
'
H
Common synonyms: hydrogen phosphide, phosphorus trihydride,
phosphoretted hydrogen, phosphane
CAS registry number: 7803-51-2
RTECS registry
number: SY7525000
United Nations
number: UN 2199
Conversion factor: 20°C, 1 ppm = 1.41 mg/m3 and
1 mg/m3 = 0.71 ppm, approximately.
Metal phosphides
Name: trizinc aluminium trimagnesium
diphosphide phosphide diphosphide
Chemical formula: Zn3P2 AlP Mg3P2
Structural Zn = P-Zn-P Al equiv. P Mg = P-Mg-P
formula: = Zn = Mg
Common synonyms: zinc phosphide magnesium
phosphide
CAS registry 1314-84-7 20859-73-8 12057-74-8
number:
RTECS number: ZH4900000 BD1400000 OM4200000
United Nations 1714 1397/3048 2011
number:
Trade names and presentations
Registered Trade Presentation
Name
Aluminium phosphide Alutal
Celphide Tablets
Celphine Tablets
Celphos Tablets
Delicia Gastoxin
Detia Gas-Ex-B Bags
Detia Gas-Ex-P Pellets
Detia Gas-Ex-T Tablets
"L" fume Tablets
Phosfume Pellets & tablets
Phostek Pellets & tablets
Phostoxin Pellets, tablets,
"Prepacs", rounds &
strips
Quickfos Pellets & tablets
Zedesa Bags, pellets &
tablets
Magnesium phosphide Detiaphos Pellets
Mag-disc Plates
Magtoxin Pellets, tablets &
rounds
1.2 Physical and Chemical Properties
Phosphine is a colourless gas at room temperature and normal
atmospheric pressure. It is odourless when pure at concentrations up
to 282 mg/m3 (200 ppm), a highly toxic level. The "garlicky" odour
of technical phosphine depends on the presence of odoriferous
impurities and is usually detectable at concentrations in the range
0.14-7 mg/m3. The autoignition temperature of pure phosphine is
38°C, but the presence of impurities, particularly diphosphine
(PH2-PH2), often causes the technical product to ignite spontaneously
at room temperature and it forms explosive mixtures with air at
concentrations greater than 1.8%. Oxidation of phosphine yields water
and phosphorus oxides or oxyacids.
Phosphine is sparingly soluble in water (about 2.5% v/v at about 20°C)
but is soluble at 2.5-15% v/v in most organic solvents at ambient
temperatures. It has an intense ultraviolet absorption in the
185-250 nm region. Phosphine is corrosive to metals, particularly
copper and copper alloys. Electrical and other equipment may be
severely damaged during fumigation. Contact with hot surfaces in the
absence of oxygen causes phosphine to break down to phosphorus and
hydrogen.
Trimagnesium diphosphide and aluminium phosphide hydrolyse readily in
water to yield phosphine:
2AlP + 6H2O = 2PH3 + 2Al(OH)3
Mg3P2 + 6H2O = 2PH3 + 3Mg(OH)2
Zinc phosphide hydrolyses in acid environments:
Zn3P2 + 6H + = 2PH3 + 3Zn+ +
Technical phosphine may contain up to 5% diphosphine and other
impurities such as methane, methyl phosphine, and arsine. For use in
the electronics industry, phosphine may be compressed as a mixture
with nitrogen. Phosphine released from fumigant preparations may
contain ammonia.
Zinc phosphide in bulk usually has a purity of 80%, the remainder
consisting mainly of zinc oxide, metallic zinc, and red phosphorus.
Pastes for incorporation into baits for use as a rodenticide usually
contain 2.5% or 5% active ingredient. Commercial preparations for
fumigation usually contain about 57% of aluminium phosphide or 34% of
trimagnesium diphosphide as active ingredient.
1.3 Analytical Methods
Gas chromatography is the most sensitive method for the determination
of the phosphine content of air samples. Usually, samples are desorbed
from a solid absorbent coated with mercury (II) cyanide, although
samples taken in syringes, gas bags, or tonometers can be used. The
sensitivity depends on the type of detector.
Phosphine levels in air may be determined by trapping phosphine by
absorption or reaction, and subsequently analysing the desorbed or
reacted sample with mercury (II) chloride, followed by the addition of
potassium iodide and then excess standard iodine solution.
Back-titration of the excess iodine with thiosulfate is used to
quantify the phosphine.
Alternatively, mercury (II) cyanide on silica gel collects phosphine
quantitatively and holds 80% of the phosphine during storage for 2
weeks. The phosphine is released for gas chromatographic analysis by
treatment with alkaline sodium borohydride solution or is oxidized
(using a hot acid permanganate solution) to phosphate, which is
measured using the phosphomolybdate colorimetric technique.
Liquid impingers/bubblers containing a variety of solutions can be
used to collect and react phosphine for quantification by
colorimetry/spectrophotometry, by conductance, or by potentiometric
titration. Classical colorimetric techniques are the development of
the red-orange complex with silver diethyldithiocarbamate, which can
be measured at 465 nm, or the oxidation by permanganate to phosphate
which is then reacted with a solution of ammonium molybdate in
concentrated sulfuric acid, extracted with toluene-isobutanol, reduced
with tin (II) chloride, and measured as the phosphomolybdate complex
at 625 nm. The first method suffers from arsine interference and the
second also measures any phosphorus species that are oxidized to
phosphate by oxalic acid/permanganate treatment.
1.4 Production and Uses
Phosphine is manufactured by the hydrolysis of metal phosphides, by
the electrolysis of phosphorus in the presence of hydrogen, or by the
phosphorus-steam reaction. It is produced incidentally by the
hydrolysis of impurities in calcium carbide, ferrosilicon, and
spheroidal graphite iron. Metal phosphides are produced by the
reduction of phosphates, by a direct reaction between the metal and
phosphorus vapour or amorphous phosphorus, or by an exchange reaction
between the metal and another metal phosphide.
Phosphine is used in the synthesis of organophosphines and organic
phosphonium derivatives and as a dopant in the manufacture of
semiconductors. Aluminium or magnesium phosphide are used as
formulations prepared for fumigation in pest control, and zinc
phosphide, as a powder or paste, is used as a rodenticide.
2. SUMMARY AND EVALUATION
2.1 Human Exposure to Phosphine and Metal Phosphides
Exposure of the skin, the eyes, or the respiratory tract may occur.
There may be mild irritation of the mucous membranes, but significant
absorption occurs only via the lungs. Metal phosphides and their
preparations may be ingested accidentally or with suicidal intent. In
occupational situations where phosphine is produced deliberately or
known to be produced, safe working practices can reduce exposure to
low levels. In many countries, fumigation and re-entry procedures are
regulated to prevent exposure. Occupational exposure to toxic levels
has occurred in circumstances where phosphine is produced
incidentally. Members of the public have been exposed as a result of
leaks from fumigated warehouses and from the holds of ships or barges.
There may be exposure from the consumption of fumigated foodstuffs.
2.2 Fate in the Environment
Phosphine released into the atmosphere reacts principally with the HO*
radical to form HOP*. The eventual products will be water and
phosphorus oxyacids. Phosphine is also removed from air by soils and
oxidized to orthophosphate. Zinc phosphide disappears from soils of
50% or more water content in less than 5 weeks, and the majority is
recoverable as orthophosphate.
2.3 Uptake, Metabolism, and Excretion
Phosphine is absorbed readily through the lungs and produces early
symptoms in the brain and liver, suggesting that it is rapidly
distributed at least to these organs. After peak exposure, phosphine
is excreted in the expired air and some is oxidized to phosphite and
hypophosphite ions, which are excreted in the urine. Metal phosphides
may hydrolyse to produce phosphine, which may be absorbed through the
intestine after ingestion. Some zinc phosphide has been shown to reach
the liver and kidneys intact after ingestion and to hydrolyse slowly
in the tissues to phosphine and zinc salts. Hydrolysis of metal
phosphides on the skin could lead to the evolution of gaseous
phosphine, which could then be absorbed by inhalation. Little
percutaneous absorption of metal phosphides occurs.
2.4 Effects on Organisms in the Environment
Phosphine is not normally present in the environment and any that is
released into it will be rapidly diluted and subsequently oxidized so
that its effects are minimal. Phosphine and metal phosphides are
deliberately released into confined locations for the purpose of
eliminating certain pests. Phosphine has been demonstrated to be
effective against many species of arthropod, though the susceptibility
of the different developmental stages may vary. In general, larvae are
more susceptible than adults; pupae tend to be less susceptible and
eggs least susceptible. Diapausing larvae may be relatively resistant.
Zinc phosphide baits can be laid for rodent pests and the effect on
non-target species can be minimized by applying a knowledge of the
habits and runs, or by using magnesium or aluminium phosphide
preparations in the burrows of target pest species. Animals killed by
metal phosphides have been demonstrated to be nontoxic to carrion
eaters.
2.5 Effects on Animals and Human Beings
The 4-hour LC50 for phosphine in rats is 15 mg/m3. Quoted oral LD50
values for zinc phosphide in the rat are in the range of 30-40 mg/kg
body weight.
Acute exposure to phosphine produces similar effects in man and
animals. Concentrations approaching 3000 mg/m (2000 ppm) are rapidly
fatal. Concentrations of about 700 mg/m3 (500 ppm) cause death in
0.5-1 hour. Concentrations around 200 mg/m3 (150 ppm) will produce
serious effects after 0.5-1 hour; concentrations around 10 mg/m3 have
no serious effects with the same exposure duration. The predominant
pathological feature in acute fatal cases is pulmonary oedema. Severe
non-lethal cases complain of pain and tightness in the chest.
Neurological abnormalities include headache, vertigo, tremors, and
unsteady gait, and may progress to convulsions, coma, and death; they
may mimic alcoholic intoxication. Gastrointestinal symptoms include
loss of appetite, thirst, nausea, vomiting, diarrhoea, epigastric
pain, and jaundice. Other effects described include thrombocytopenic
purpura and hypotension.
While phosphine itself is not cumulative, its effects appear to be, so
that the lethal dose of inhaled phosphine after several days'
treatment with short, sublethal exposures is lower than in animals
without pretreatment. Deaths have occurred in man as a result of
repeated daily exposures to concentrations well below acutely
injurious concentrations.
The effects of suicidally ingested zinc phosphide are well known. In
most cases, the ingestion of more than 20 g is fatal: most people who
ingest less than 20 g survive. Clinical features include metabolic
disturbances (metabolic acidosis, hypocalcaemic tetany), congestion in
many organs, haemorrhagic changes in the intestines and serous
membranes, and clinical signs and pathological features of liver and
kidney failure.
There have been no long-term studies on the effects of phosphine or
metal phosphides on animals or man and there are no data relating to
mutagenicity, teratogenicity, or carcinogenicity.
3. CONCLUSIONS AND RECOMMENDATIONS
Phosphine is a highly toxic gas and considerable care needs to be
taken during production, storage, and use, and where it may arise in
the course of other procedures. However, it presents no hazard to the
general population and accidental emissions into the environment are
most unlikely to cause persistent or high concentrations, or to lead
to accumulation. Apart from its use in chemical synthesis and
electronics, phosphine is used chiefly for its toxic effects. Its
chemical simplicity and rapid dispersion and conversion into simple
inorganic molecules of low toxicity make it very suitable for this
purpose.
Metal phosphides, if carefully used, present little risk to those who
use them, or to the general population, or to important non-target
species in the environment. Administrative controls are necessary to
prevent easy access by children, persons with diminished
responsibility, or those with suicidal intent.
4. HUMAN HEALTH HAZARDS, PREVENTION AND PROTECTION, EMERGENCY ACTION
4.1 Main Human Health Hazards, Prevention and Protection, First Aid
The main hazard to man is the possibility of unrecognized occupational
exposure to phosphine causing acute poisoning. Neither the smell nor
sensory irritation can be relied upon for warning of toxic
concentrations, especially in the presence of other fumes, gases, or
vapours. Another important hazard is the possibility of members of the
public being affected by phosphine leaking from fumigated warehouses
or cargoes, or evolving spontaneously from cargoes of ferrosilicon. In
agricultural communities, children may be at risk from the accidental
consumption of bait poisoned with zinc phosphide.
The human health hazards are listed on the International Chemical
Safety Card, on pages 22-26, together with preventive and protective
measures and first aid recommendations.
4.1.1 Advice to physicians
In the case of exposure to phosphine, rapid recovery will usually
occur when the patient is moved to fresh air. No specific antidote is
known. Hypotension has been described following exposure, but signs of
peripheral vasoconstriction are not normally present and plasma
expanders are probably not required. Tests may indicate disordered
liver function. If supportive treatment is successful, full recovery
usually follows. After recovery, a period of rest and avoidance of
alcohol is advisable until the affected organs have fully recovered.
After severe exposure to the vapour, the risk of delayed pulmonary
oedema may be sufficient to require admission of the patient to
hospital for observation for 24-48 h. An initial chest X-ray will be
useful for later assessment of the development of pulmonary oedema.
Bronchodilators by nebulizer or metered dose aerosol may be given to
reduce bronchospasm and dyspnoea. Where there are immediate
respiratory symptoms suggestive of lower airway exposure, it may be
beneficial to administer steroids to minimize chemical pneumonitis and
scarring. Steroids may administered by intravenous injection of
methylprednisolone in doses up to 30 mg/kg body weight initially, with
subsequent smaller doses, or by use of steroids in metered-dose
aerosol form at several times the normal maintenance dosage.
Prophylactic antibiotics are generally indicated in all but mild
cases, since secondary bacterial infection of the airways often
occurs.
If pulmonary oedema develops, the patient should be nursed with the
trunk upright and oxygen should be administered. Diuretics, morphine,
and theophylline derivatives are of little benefit, since the oedema
is the result of an exudate rather than a transudate arising from
raised pulmonary capillary pressure. If further measures are
necessary, intermittent positive pressure ventilation combined with
bronchial toilet and suction are the important elements of treatment.
In the event of ingestion of metal phosphides, tracheal intubation and
gastric lavage with sodium bicarbonate solution may remove some of the
material and may reduce the amount of phosphine evolved. Potassium
permanganate has been used in an attempt to oxidize the phosphide. On
a theoretical basis, the administration of activated charcoal may
adsorb some of the evolved phosphine and there is a possibility that
the administration of medicinal paraffin may reduce the hydrolysis and
absorption of the phosphide itself.
Otherwise, treatment should be symptomatic and supportive with
particular attention to liver and kidney function.
4.1.2 Health surveillance advice
It is advisable for persons with pre-existing gastrointestinal or
liver disease to be excluded from work with phosphine. Wherever
measured exposures approach the occupational exposure limit or where
exposure levels require the use of personal respiratory protection
equipment, it is wise to measure pulmonary and liver function
routinely.
4.2 Explosion and Fire Hazards
Phosphine (unless of very high purity) ignites spontaneously in air at
ambient temperatures at concentrations above 1.8%. Where emissions
exceed this concentration, controlled combustion is the best way of
preventing accidental fires and explosion. Such concentrations are not
normally reached during fumigation. Fire-fighters should wear
compressed-air breathing apparatus.
4.3 Storage
Phosphine admixed with inert gases in cylinders should be stored in
accordance with the usual practices for compressed gases in a cool,
dry, well ventilated place. For industrial purposes, phosphine may be
stored in a gas-holder, suitably constructed to resist corrosion, from
which air can be excluded. Large quantities of phosphine can
constitute a major hazard and appropriate installations are required
for the control of such hazards. Metal phosphides should be stored in
sealed, polyethylene-lined drums in a well ventilated, dry warehouse.
Drums should be carefully handled to avoid puncturing. Formulated
commercial preparations of metal phosphides should be stored dry in a
locked cupboard out of the reach of children.
4.4 Transport
In case of accident during transport by road, stop the engine and
remain up-wind. Do not apply water to spilled metal phosphides. If a
gas cloud drifts towards an inhabited area, warn the inhabitants and
evacuate areas close to the spillage, if this can be done without
risking exposure.
4.5 Spillage and Disposal
Surplus gas or leakages of gas from cylinders can be vented slowly to
air in a safe open area, or the gas can be burnt off through a
suitable burner in a fume cupboard. It may be spontaneously flammable
and jets from leaking valves may ignite. Large spillages of magnesium
or aluminum phosphides or preparations formulated from them should be
kept dry and shovelled into containers that can be sealed by persons
equipped with respiratory protective equipment effective against
phosphine. The containers should be removed to a secure site where
they can be placed open in a deep pit, kept moist, and allowed to
hydrolyse slowly until all the phosphine has evolved. Residues may
then be disposed of by deep burial in an approved landfill. The
contaminated area should be washed down with copious amounts of water.
Small spills may be allowed to hydrolyse in situ if the public and
domestic animals can be kept away.
Spillages of zinc phosphide should be collected in sealable containers
by persons wearing respiratory protection and the material should be
disposed of by high-temperature incineration, or made chemically inert
in accordance with advice from an expert.
Combustible packages can be incinerated at high temperatures or
disposed of in deep landfill.
5. HAZARDS FOR THE ENVIRONMENT AND THEIR PREVENTION
Phosphine is used deliberately in the environment to eliminate pests,
but only where the environment has been extensively modified by
industrial or agricultural activities. Its use does not impose any
recognized environmental hazard apart from this.
6. INTERNATIONAL CHEMICAL SAFETY CARD
This card should be easily available to all health workers
concerned with, and users of, phosphine and metal phosphides. It
should be displayed at, or near, entrances to areas where there is
potential exposure to phosphine or phosphides, and on processing
equipment and containers. The card should be translated into the
appropriate language(s). All persons potentially exposed to the
chemical should also have the instructions on the chemical safety
card clearly explained.
Space is available on the card for insertion of the National
Occupational Exposure Limit, the address and telephone number of
the National Poison Control Centre, and for local trade names.
INTERNATIONAL CHEMICAL SAFETY CARD
PHOSPHINE
(Hydrogen phosphide, phosphorus trihydride, phosphoretted hydrogen, phosphane)
(CAS Registry No. 7803-51-2)
PHYSICAL PROPERTIES OTHER CHARACTERISTICS
Relative molecular mass 34 A colourless gas at ambient temperature and
Melting point -133.5°C pressure; it is odourless in the pure state but
Boiling point -87.4°C technical phosphine characteristically has a
Relative vapour density 1.17 "fishy" or "garlicky" odour due to impurities
Spontaneous ignition temperature 38°Ca
Lower explosive limit 1.8%
a Varies with the presence of impurities.
TRIZINC DIPHOSPHIDE
(Zinc phosphide)
(CAS Registry No. 1314-84-7)
PHYSICAL PROPERTIES OTHER CHARACTERISTICS
Relative molecular mass 258.1 A grey solid
Melting point sublimes
Density (13°C) 4.55
INTERNATIONAL CHEMICAL SAFETY CARD (cont'd).
ALUMINIUM PHOSPHIDE
(CAS Registry No. 20859-73-8)
PHYSICAL PROPERTIES OTHER CHARACTERISTICS
Relative molecular mass 57.96 A grey/yellow solid
Melting point > 1350°C
Density (25°C) 2.85
TRIMAGNESIUM DIPHOSPHIDE
(Magnesium phosphide)
(CAS Registry No. 12057-74-8)
PHYSICAL PROPERTIES OTHER CHARACTERISTICS
Relative molecular mass 134.87 A grey solid
Melting point > 750°C
Density (25°C) 2.1
INTERNATIONAL CHEMICAL SAFETY CARD (cont'd).
HAZARDS/SYMPTOMS PREVENTION AND PROTECTION FIRST AID
PHOSPHINE GAS FUMES
SINGLE EXPOSURE
SKIN & EYES: No local effects or Full-face mask protects eyes Not required
significant absorption
INHALATION: Irritation of respiratory Avoid exposure by enclosure, Move patient to fresh air and keep
tract; effects on the central nervous exhaust ventilation, or suitable him quiet; if breathing has stopped,
system include ataxia which may mimic respiratory protective equipment; apply artificial respiration; if
drunkenness and hypotension; nausea odour may not warn of toxic pulse is feeble or there is clouding
and upper gastrointestinal symptoms concentrations of consciousness, lie patient down
may occur; eventually, unconsciousness, with the feet raised
respiratory depression, and death
may occur
INGESTION: Not possible
REPEATED EXPOSURE
There is some evidence that effects may summate with the residual effects of previous exposure
INHALATION: There is a possibility As for single exposure
of upper gastrointestinal symptoms
and headache
SKIN & EYES: No recognized chronic
effects
INTERNATIONAL CHEMICAL SAFETY CARD (cont'd).
HAZARDS/SYMPTOMS PREVENTION AND PROTECTION FIRST AID
METAL PHOSPHIDES
SINGLE EXPOSURE
SKIN: No evidence of irritation, Avoid exposure: handle pellets, Work in the open or in a well-ventilated
direct absorption; hydrolysis in disks, etc., using gloves or the place; brush off any dry material and
atmospheric moisture or perspiration wrapper; dry exposed skin and wear then wash or shower thoroughly using soap
may yield gaseous phosphine, which gloves before mixing powdered if available; if there are signs of phosphine
could be inhaled material; wash thoroughly in a inhalation, see International Chemical Safety
well-ventilated place after Card for phosphine
handling
EYES: Mechanical and chemical Avoid exposure; keep contaminated Rinse thoroughly with a gentle flow of water for
irritation gloves and hands away from face; at least 15 minutes
handle powder so as to minimize
dust; wear goggles
INHALATION: Irritation of respiratory Handle powdered material so as to See International Chemical Safety Card for
tract both directly and by the minimize dust; ensure good local phosphine
evolution of phosphine; possible and general ventilation.
systemic effects from phosphine Respiratory protective equipment,
absorption (see International Chemical if required, should be effective
Safety Card for phosphine) against both phosphide dusts and
gaseous phosphine
INTERNATIONAL CHEMICAL SAFETY CARD (cont'd).
HAZARDS/SYMPTOMS PREVENTION AND PROTECTION FIRST AID
INGESTION: Nausea, abdominal Keep all preparations locked up Induce vomiting in conscious
pain, and vomiting; circulatory and out of reach of children; do patients who have not vomited; give
collapse, altered consciousness, not eat or smoke while using activated charcoal as a suspension
coma, convulsions; signs of gross preparations and wash hands after in water by mouth, repeat after vomiting,
liver and kidney disturbance use and obtain medical attention
REPEATED EXPOSURE
There is some evidence that effects will summate with the residual effects of previous exposures
7. CURRENT REGULATIONS, GUIDELINES, AND STANDARDS
The information in this section has been extracted from the
International Register of Potentially Toxic Chemicals (IRPTC) legal
file. The reader should be aware that regulatory decisions about
chemicals taken in a certain country can only be understood in the
framework of legislation in that country.a
A full reference to the original national document from which the
information was extracted can be obtained from IRPTC. When no
effective date appears on the IRPTC legal file, the year of the
reference from which the data are taken is indicated by (r).
7.1 Exposure Limit Values
Some exposure limit values are given in the following table.
7.2 Specific Restrictions
There are restrictions on the use of phosphine as a pesticide in
Brazil, Czechoslovakia, the Federal Republic of Germany, Sweden, and
the USSR.
In Czechoslovakia and Japan, phosphine and phosphides are classified
as dangerous poisonous substances.
In the Federal Republic of Germany, the level of phosphine in air
emissions may not exceed 1 mg/m3 at a mass flow rate of 10 g/h.
Phosphine is classified as harmful in water and appropriate measures
are required to protect water supplies.
In the European Economic Community, phosphine is listed as a dangerous
substance in quantities greater than 100 kg.
In the USA, commercial chemical products containing phosphine are
classified as acute hazardous wastes, and solid waste (except
domestic) containing phosphine is classified as hazardous waste.
7.3 Labelling, Packaging, and Transport
The United Nations classifies phosphine as a hazardous gas
(compressed) with the subsidiary risks of a flammable liquid and a
poisonous substance.
a The regulations and guidelines of all countries are subject to
change and should always be verified with the appropriate regulatory
authorities before application.
EXPOSURE LIMIT VALUES
Medium Specification Country/ Exposure limit description Value Effective
organization date
AIR Occupational Australia Threshold limit value (TLV) 1985 (r)
- Time-weighted average (TWA) 0.4 mg/m3
Belgium Threshold limit value 1987 (r)
- Time-weighted average 0.4 mg/m3
- Short-term exposure limit (STEL) 1 mg/m3
Bulgaria Maximum permissible concentration (MPC) 1985
- Time-weighted average 0.1 mg/m3
Canada Threshold limit value 1985 (r)
- Time-weighted average 0.4 mg/m3
- Short-term exposure limit 1 mg/m3
Czechoslovakia Maximum allowable concentration (MAC) 1985
- Time-weighted average 0.1 mg/m3
- Ceiling value (CLV) 0.2 mg/m3
Finland Maximum permissible concentration 1985 (r)
- Time-weighted average 0.1 mg/m3
AIR Occupational German Maximum allowable concentration 1985 (r)
Democratic - Time-weighted average 0.1 mg/m3
Republic - Short-term exposure limit 0.3 mg/m3
EXPOSURE LIMIT VALUES (cont'd).
Medium Specification Country/ Exposure limit description Value Effective
organization date
Germany, Maximum work-site concentration (MAK) 1987 (r)
Federal - Time-weighted average 0.15 mg/m3
Republic of - Short-term exposure limit 0.3 mg/m3
(5 minutes, 8 ×/shift)
Italy Threshold limit value 1985 (r)
- Time-weighted average 0.4 mg/m3
Netherlands Maximum limit (MXL) 1987 (r)
- Time-weighted average 0.4 mg/m3
- Short-term exposure limit 1.5 mg/m3
Poland Maximum permissible concentration 1985 (r)
- Ceiling value 0.1 mg/m3
Romania Maximum permissible concentration 1985 (r)
- Time-weighted average 0.2 mg/m3
- Ceiling value 0.5 mg/m3
Sweden Hygiene limit value (HLV) 1988
- Time-weighted average 0.4 mg/m3
- Short-term exposure limit 1.4 mg/m3
(15-minutes time-weighted average)
Switzerland Maximum work-site concentration 1987 (r)
- Time-weighted average 0.15 mg/m3
EXPOSURE LIMIT VALUES (cont'd).
Medium Specification Country/ Exposure limit description Value Effective
organization date
United Recommended exposure control limit (RECL) 1987 (r)
Kingdom - Time-weighted average 0.4 mg/m3
- Short-term exposure limit 1 mg/m3
(10-minutes time-weighted average)
USA (ACGIH) Threshold limit value 1987 (r)
- Time-weighted average 0.4 mg/m3
- Short-term exposure limit 1 mg/m3
USA (OSHA) Permissible exposure limit (PEL) 1987 (r)
- Time-weighted average 0.4 mg/m3
USSR Maximum allowable concentration 1977
- Ceiling value 0.1 mg/m3
Yugoslavia Maximum allowable concentration 1985 (r)
- Time-weighted average 0.1 mg/m3
AIR Ambient USSR Maximum allowable concentration 1984
- Daily average 0.001 mg/m3
- Once daily 0.01 mg/m3
WATER Surface USSR Maximum allowable concentration 0.1 mg/litre 1985 (r)
(surface water for fishing)
EXPOSURE LIMIT VALUES (cont'd).
Medium Specification Country/ Exposure limit description Value Effective
organization date
FOOD FAO/WHO Maximum residue limit 1982 (r)
- Flour, milled cereal products,
breakfast cereals, dried vegetables,
spices, nuts, peanuts, dried fruit,
cocoa beans, other dried foods 0.01 mg/kg
EEC Maximum residue limit 1988
- Cereals (general) 0.1 mg/kg
Brazil Acceptable limit (AL) 1985 (r)
(Specified plants) 0.01-0.1 mg/kg
Czechoslovakia Maximum residue limit 0.01-0.1 mg/kg 1978
Germany, Maximum residue limit 1984
Federal - Specified plant products 0.01-0.1 mg/kg
Republic of - Other plant products 0.01 mg/kg
- Tobacco 0.01 mg/kg
India Maximum tolerable concentration (MTC) 1976
- Specified food products 0.01-0.05 mg/kg
USSR Maximum residue limit 1984
- Food exported and imported 0.01-0.1 mg/kg
EXPOSURE LIMIT VALUES (cont'd).
Medium Specification Country/ Exposure limit description Value Effective
organization date
USA Acceptable residue limit (ARL) 1983 (r)
- Raw agricultural products: phosphine
resulting from use of zinc phosphide 0.01-0.1 mg/kg
- Raw agricultural products: phosphine
resulting from use of aluminum or
magnesium phosphides as preharvest
pest treatment 0.1 mg/kg
- Processed foods: phosphine resulting 1985 (r)
from fumigation by magnesium or
aluminum phosphides 0.01 mg/kg
BIBLIOGRAPHY
ACGIH (1986) Documentation of the threshold limit values and
biological exposure indices. Cincinnati, American Conference of
Governmental Industrial Hygienists.
CLAYTON, G.D. & CLAYTON, F.E. (1981) Patty's industrial hygiene and
toxicology. Vol. 2.4. New York, Wiley - Interscience, John Wiley &
Sons.
DUTCH ASSOCIATION OF SAFETY EXPERTS (1980) Handling chemicals
safely. 2nd ed. Dutch Chemical Industry Association, Dutch Safety
Institute.
GOSSELIN, R.E., ET AL. (1976) Clinical toxicology of commercial
products. 4th ed. Baltimore, Maryland, Williams and Wilkins Company.
IRPTC (1988) Data profile (legal file, waste disposal file,
treatment of poisoning file), Geneva, International Register of
Potentially Toxic Chemicals.
SAX, N.I. (1984) Dangerous properties of industrial materials. New
York, Van Nostrand Reinhold Company.
US NIOSH (1976) A guide to industrial respiratory protection.
Cincinnati, Ohio, US National Institute for Occupational Safety and
Health.
US NIOSH/OSHA (1985) Pocket guide to chemical hazards. Washington,
DC, US National Institute for Occupational Safety and Health,
Occupational Safety and Health Association (Publication
No. 85.114).
US NIOSH/OSHA (1981) Occupational health guidelines for chemical
hazards. 3 vol. Washington, DC, US National Institute for
Occupational Safety and Health, Occupational Safety and Health
Association (Publication No. 01.123).
WHO (1988) Phosphine and selected metal phosphides. Geneva, World
Health Organization (Environmental Health Criteria 73).